Spundyed regenerated cellulose products



3,053,678 SPUNDYED REGENERATED CELLULOSE PRODUCTS Konrad Mix, Frankfurt am Main, Fechenheim, Germany,

assignor to Cassella Farbwerke Mainkur Aktiengesellschaft, Frankfurt am Main, Fechenheim, Germany, a company of German No Drawing. Filed March 17, 1961, Ser. No. 96,381 Claims priority, application Germany Mar. 23, 1960 4 Claims. (Cl. 106-165) This invention relates to the manufacture of regenerated cellulose products spundyed with nitroaryl-hydrazone pigments.

Among the current methods for the dyeing of regenerated cellulose there is the spin dyeing with finely dispersed pigment dyes which is of utmost importance.

In producing spundyed regenerated cellulose products, such as viscose rayon, fibers and films, the coloring matter, such as pigment material, is dispersed in the spinning solution which solution is then extruded through suitable spinnerets or other shape forming devices into coagulating and subsequent processing baths before the spun or extruded products are finally dried. A colored product is thus produced.

Such a process is frequently preferred to that process wherein the products are dyed after the extrusion, coagulation and other processing steps. With spindyeing, colored or dyed products are initially provided which may be further treated without the necessity of any subsequent dyeing.

In the spin dyeing processes hitherto known there have been used as pigment dyes chiefly water-insoluble azo dyes, such as fi-hydroxy-naphthoic-acid-arylides or high-quality vat dyes.

Now, I have found that most satisfactory spundyed products of regenerated cellulose may be easily obtained from the well-known viscose spinning solutions by incorporating into the viscose spinning solutions monoor dinitroaryl-hydrazones in a finely dispersed form which conv United States Patent nuclei may be combined with each other in any way, viz. they may be condensed or directly or indirectly linked with each other.

The nitroaryl-hydrazones used according to my invention may bear additional substituents of the group con sisting of alkyl, cycloalkyl, oxyalkyl, aryl, aralkyl, carbonyl, alkoxy, aryloxy, acyl, nitro, h-alogeno, sulfonyl, amino and 212-0 radicals.

Thus, products are obtained which, depending on the constitution of the employed nitroaryl-hydrazone, are dyed in clear yellow, orange, red to brown shades, the dyeings of which distinguish themselves by excellent fastness properties to light, ironing, washing, boiling, weather etc.

This result was surprising. In particular, it could not be foreseen that the nitroaryl-hydrazones used according to my invention would be stable in the strongly alkaline viscose solution or remain unchanged in their color shade, particularly since it is known that one characteristic feature of the simple nitrophenyl-hydrazones, which is decisive for their analytical determination is that considerable al-teration of shade occurs in the presence of alkali active agents.

The nitroaryl-hydrazones which are suitable for the process of the present invention may be prepared in the known methods, such as being described in Houben-Weyl Methoden der organischen Chemie, Fourth edition, volume VII/=1, page 465, by reacting nitroaryl-hydrazines with appropriate carbonyl compounds, preferably in an acid pH-range.

Especially suited are the hydrazones of the following nitraoaryl-hydrazines:

. 2,4-dinitro-phenyl-hydrazine 2,4-dinitrophenylene-1,S-dihydrazine 2-nitro-4 (N) -methylsulfamido-phenylhydrazine 2-nitro-4 (N) -dimethylsulfamido-phenylhydrazine 2,4-dinitro-S-chloro-phenylhydrazine.

The following tables enumerate a series of such hydrazones together With the color shades obtained thereby in tain in the molecule at least 3 phenyl nuclei. The phenyl the SPH]. dyeing of viscose.

TABLE I Formulae N 02 Mono-2,4-dinitrophenylhydrazoues ot the following carbonyl Color compounds X: NO3

IfiL-NH-X 1, Benzonh nnn Yellow.

,W C 2. 4,4'-dibromobenzonhennne Do B Br N-NH-X I C 3. 4-methoxy-benzophenone- I Golden ye1low..

. O CH;

TABLE IContin1 1ed Formulae N02 MOno-2,4-dinitropheny1hydmzones or the following carbonyl Color compounds X NO:

N-NH-X ll 14. 2-acety1-dibenzofuran 0H: Golden yellow.

15. l-naphthyl-methylketone Do.

1\[TNH-X C CHs 16, Z-naphthyl-methylketone. Do.

17. l-naphthyl-phenylketone Do.

18, 2-naphthy1-phenylketone Do.

19. 4-ace** -benzop m- Orange,

20. 4-(4-acetam1nophenyl)-acetophenone -L HaC Red.

NNH--X 21. 4-(fl-chloropropionylamino)-benzophenone... Orange.

N C O-GHz-OHr-Cl H1 1 HaC-C=NNHX 22, 4-[4'-(B-chloropropionylamino)-pheny1]-acetophen0ne Red.

TABLE ICntinued Formulae N 0: Mono-2,4-dinitrophenylhydrazones o! the following carbonyl Color compounds X= NO:

lfiI-NH-X 23. Coupling product of dlazotlzed 4-aminobenzophenone with aceto- V V Yellowish brown.

acetani e. CCH':

N=N-O\ N-NH-X I! C 24. 4(4-dlmethylaminophenylazo)-benzophenone OH Orange.

al 25. 1,4-dibenzoy nhrh l Yellow.

H v l 0 0 II 26. Anthraqulnone-2-a1dehyfl CH=N-NH.X Do

C CH=NNH.X 27. 1-mnlno-anthraqulnone-2-aldehyde Red.

TABLE II TABLE II-Continued Formulae Formulae Bls-2,4-din1tro- Bls-ZA-dinitrophenylhydrazones NO phenylhydrazones N 09 the following I color of the following color carbonyl compounds carbonyl compounds X No: X= N 03 N--NHX II N-NH.X 28. 4,4-dibenzoy1- C II djphenyl. Yellow. 0

30. 1,4-dibenzoy1- naphthalene. D0.

I] 1% El NNH.X N-NH-X IfiI-NH-X 29. 1,5-dlbenzoy1- naphthalene. Do.

u N-NH-X P'LE II Further nltro-phenylhyd azones Formulae v v I Color 3iilsl fiiegzzgghenone-(2-nitro-4-Nmethy1snlfamido-phenyl- Golden yellow.

H;C.NH.O4S --N0a A 32. BSHZODhBIlOllB-( Z -nitro 4 N,N-dlmethy1su1famido- V D phenylhydrazone). NHN=C 33. Benzophenone (2,4 dinitro 5 -ch1orop'heny1hydra- Yellow zone).

34. Condensation product of 1 mol 4,6-d1n1trophenylene 1,3-dihydmzlne with 2 mols of benzophenone.

35. Condensation product of 1 mol 4,6-'dinitro-pheny1ene- 1,3-dihydrazine with 2 mole of benzaldehyde.

36. Condensation product of 1 mol 4,6-dinitro-phenylene- 1,3-dihydrazine with 2 mole of anisaldehyde.

37. Condensation product 0! 1 mol 4,6-din1tro-pheny1ene- 1,3-dihydrazine with 1 mol benzophenone and 1 mol acetone.

39. Condensation productoi 1 mol 4,64iinltro-phenylene- 1,3-di hydrazine with 1 mol benzophenone and 1 mol acetophenone.

Greenish yellow.

Golden yellow.

Red.

Yellow. r

Golden yellow.

TABLE Ills-Continued Further nitro-phenylhydrazones Formulae Color O1N N0, 40. Condensation product of 1 mol 4,64itnitro-phenylene- 1.3-dlhydrazlne with 1 mol benzophenone and 1 Do. mol propion-aldehyde. C=NNH -NHN=CHCHr-CH1 OzN N01 41. Condensation product of 1 mol 4,6-dinitro-phenylene- 1,3dlhydrazine with 1 mol benzophenone and 1 Do. mol croton-aldehyde. C=NNH NHN=CH--CH=CHC H:

OzN "N02 42. Condensation product ofl mol4,6'dinitro-phenylene- CHz-CH,

1,3-dihydrazine with 1 mol benzophenone and 1 Yellow. mol cyclo-hexanone. C---N-N H NHN=C /CH GHQ-CH2 43. Condensation product of 1 mo14,6-dinitro-phenylene- OzN- NO;

1 3-dihydrazlne with 1 mol -phenylacetophenone CH; CH; Golden yellow. and 1 mol acetone. I

C=N-NH NHN=O f 44. Condensation product of 2 mols benzophenone-(2,4- OzN N02 dinltro-5-chlorophenylhydrazoue) with 1 mol 4,4- Brown. diamino-diphenyl.

/C=NNH NH C) f 45. Condensation product of 2 mols 2,4-dinitro-5-(di- OQN- N;

phenylmethylene hydrazine) phenylhydrszine Yellow. with 1 mol glyoxal.

C=NNH NHN=CH LO r 46. Condensation product of 2 mols 2,4-dinitro--(di- OaN- N0,

pliglrlnl l meliylegni hydrazino) phenylhydrazine Do.

a e w mm c y G=N-NH NHN=C icy 2 Nitroaryl-hydrazones for the spin dyeing of viscose are preferably prepared in form of an aqueous paste which is obtained by grinding finely the pigment up to a medium granular size of about 1 in the presence of water. Common dispersing and grinding auxiliaries can be added to the aqueous dispersion.

The introduction of the dye paste into the viscose may be made at any stage of its preparation.

The following example will further illustrate how my invention may be carried out in practice, but the invention is not restricted to this example. The parts given are by weight and the percentages are percentage-byweight.

Example 1000 parts viscose spinning solution prepared from shredded cellulose, sodium hydroxide, carbon disulfide and water, corresponding to 85 parts regenerated cellulose, are admixed at a temperature of -25 C. with 4.25 parts pigment dye paste which has been prepared according to the method described hereinafter, and the mixture is stirred for half an hour. The mass is then spun or extruded in the usual manner or a spinning machine. The coagulation of the viscose is efiected in a sulfuric acid precipitation bath, then the material thus spun is aftertreated in the usual manner with water and solutions of diluted alkali, diluted acid and, if desired, with a solution of sodium hypochlorite.

To prepare the pigment dye paste parts of one of the before-mentioned nitroaryl-hydrazones are ground together with 25 parts sodium dinaphthyl-methane-disultomato and about 300 parts of water, until a particle size of about 1/.L is obtained.

Then the dyestuif content is adjusted to a content of 20% of the total mixture by means of water.

What I claim is:

1. A process of manufacturing spundyed regenerated cellulose products from viscose spinning solutions comprising the steps of incorporating into the viscose spinning solution nitroaryl-hydrazones selected from the group consisting of rnonoand dini-troaryl-hydrazones in a finely dispersed form, said hydrazones containing in the molecule at least 3 phenyl nuclei, and coagulating the resultant spinning solution in an acid bath.

2. A process of manufacturing spundyed regenerated cellulose products from viscose spinning solutions comprising the steps of incorporating into the viscose spinning solution nitroaryl-hydrazones selected from the group consisting of monoand dinitroaryl-hydrazones in form of a finely dispersed dye paste, said hydrazones containing in the molecule at least 3 phenyl nuclei, and coagulating the resultant spinning solution in an acid bath.

3. A process of manufacturing spundyed regenerated cellulose products from viscose spinning solutions comprising the steps of incorporating into the viscose spinning solution nitroaryl hydrazones selected from the group consisting of monoand dinitnoaryl-hydrazones in a finely dispersed form, said hydrazones containing in the molecule at least 3 phenyl nuclei and hearing at least one of the substituents of the group consisting of alkyl, cycloalkyl, oxyalkyl, \aIyl, aralkyl, carbonyl, alkoxy, aryloxy, acy], nitro, halogeno, sulfonyl, amino and azo radicals, and coagulating the resultant spinning solution in an acid bath.

4. Spundyed regenerated cellulose products containing 10 2,948,721

14 finely dispersed nitroarylwhydrazones selected from the group consisting of monoand dini-troaryl-hydrazones, said hydIazo-nes containing in the molecules at least 3 phenyl nuclei.

References Cited in the file of this patent UNITED STATES PATENTS Armento et a1 Nov. 3, 1959 Haubrick et -al. July 5, 1960 Frey Aug. 9, 1960 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N00 3,053,678 September 11,, 1962 Konrad Mix It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected belowa Column 10 under item 36 for the terminal carbon "C?" on the right-hand nucleus read H column 12, item 43, the formula should appear as shown below instead of as in the patent:

O N N0 CINWNH NH-N=C Signed and sealed this 12th day oi March 19630 (SEAL) Attest:

ESTON G, JOHNSON DAVID e LADD Attesting Officer Commissioner of Patents 

1. A PROCESS OF MANUFACTURE SPUNDYED REGENERATED CELLULOSE PRODUCTS FROM VISCOSE SPINNING SOLUTIONS COMPRISING THE STESPS OF INCORPORATING INTO THE VISCOSE SPINNING SOLUTIONS NITROARYL-HYDRAZONES SELECTED FROM THE GROUP CONSISTING OF MONO- AND DINITROARYL-HYDROZONES IN A FINELY DISPERSED FORM, SAID HYDROZONES CONTAINING IN THE MOLECULE AT LEAST 3 PHENYL NUCLEI, AND COAGULATING THE RESULTING SPINNING SOLUTION IN AN ACID BATH. 